Calcium fortification of bread dough

ABSTRACT

Calcium additives useful for fortifying baked goods, such as bread products, with calcium are disclosed. The calcium additives are particularly useful for fortifying leavened baked goods with calcium. Methods for preparing the calcium additives and using the calcium additives to fortify baked goods are also disclosed. Generally, the calcium additives comprise suspensions of calcium carbonate in acidic aqueous solutions such as citric acid solutions.

This application is a continuation-in-part of U.S. patent applicationSer. No. 10/770,715, filed Feb. 2, 2004.

FIELD OF INVENTION

The present invention relates generally to compositions and methods forenriching foods with calcium. More specifically, the present inventionrelates to suspensions of calcium carbonate in acidic aqueous solutionsthat are useful for enriching the calcium content of baked goods,particularly leavened bread products.

BACKGROUND OF THE INVENTION

Calcium is an essential nutrient and the most abundant mineral in thehuman body. Calcium plays a vital role in building healthy teeth andbones, blood clotting, muscle contraction, nerve function and heartfunction. In addition to these benefits, it has recently been suggestedthat calcium reduces the risk of recurrence of colon polyps. See BaronJ. A. et al. New England Journal of Medicine 1999; 340: 101-107.

Most importantly, calcium reduces the risk of bone loss caused byosteoporosis in both men and women, a condition that afflicts more than44 million individuals in the United States alone. With an agingpopulation in the United States, it is estimated that the figure willrise to more than 61 million by the year 2020. This growing healthcrisis is largely a result of calcium deficiency in the diet.

In recognition of the benefits of calcium, doctors recommend high dailycalcium intakes for people of all age groups. For example, the NationalAcademy of Sciences (“NAS”), Institute of Medicine recommends the dailycalcium intakes shown below. National Institute of Sciences, Instituteof Medicine Dietary Reference Intake (DIR) of Calcium for Men And WomenAge DRI 1-3 years 500 mg 4-8 years 800 mg 9-18 years 1,300 mg 19-50years 1,000 mg 51 years and up 1,200 mg

Similarly, the United States Recommended Daily Allowance (“USRDA”) ofcalcium for adults is 800 to 1,400 mg.

It has been estimated, however, that half of all Americans do notconsume sufficient amounts of calcium. More troubling, 80% of women, thegroup at highest risk for developing osteoporosis, do not consume enoughcalcium. Further, estimates reveal that only 20% of girls and 50% ofboys between the ages of 9 and 19 get the recommended daily intake ofcalcium. This is particularly troubling since 90% of human bone mass isdeveloped by age 17. Thus, proper calcium consumption during these yearsis critical for preventing the onset of osteoporosis in later life.

For many individuals, it is difficult to meet the large daily intake ofcalcium suggested by physicians from dietary sources alone. This calciumdeficiency is due in part to the low calcium content of foods thatcomprise the typical diet. Multi-vitamins and calcium supplement tabletsrepresent an important alternative to dietary calcium. However, mostcommercially available multi-vitamin tablets provide only 10 to 20% ofthe recommended dose calcium. Calcium supplement tablets provide morecalcium, typically 500 to 600 mg. To meet the recommendations, twotablets must be consumed daily. Unfortunately, too few people adhere tocalcium supplement regimens, owing in part to the fact that presentlyavailable calcium tablets are very large and difficult or uncomfortableto swallow.

Milk is widely recognized as a good source of calcium. Several glassesof milk must be consumed each day in order to obtain sufficient calcium.For example, 9 to 18 year old children must consume at least fourglasses of milk daily in order to receive the proper amount of calcium.However, the popularity of carbonated beverages has resulted in adecline in milk consumption among children. Further, many individualswho suffer from lactose intolerance cannot drink milk. Other individualschoose not to drink milk due to its high saturated fat content.

Health conscience consumers are increasingly demanding alternativesources of calcium from dietary products. This is evident from a recentstudy by Mintel's International showing an increase in food and drinkproducts sold in North America which advertise calcium content.According to that study, 32% of dairy products, including milk andcheeses, 27% of beverages, and 18% of snacks advertise calcium content.In contrast, only 5% of bakery products noted calcium content. This isunfortunate since bread and cereal products are the most ubiquitous foodsource worldwide. For example, the U.S. Department of Agricultureestimates that approximately 200 pounds of flour and cereal productswere consumed per capita in the United States in 2001, a figure whichhas been steadily growing for the past three decades. In contrast, only22 gallons of milk were consumed per capita in the United States duringthe same period. Clearly, bread products would provide an ideal vehicleto supplement dietary calcium intake.

Unfortunately, conventional breads represent a poor source of calcium.The total mineral content of wheat generally ranges from 1 to 2% byweight. The minerals present in wheat are primarily distributed in thebran and are present in the endosperm, the wheat fraction from whichmost commercial flours are produced, to a much smaller degree. Forinstance, wheat typically contains about 0.45% by weight elementalcalcium. The bran fraction contains about 0.128% by weight elementalcalcium, whereas flour fractions such as farina, patent flour, and clearflour contain less than 0.03% by weight calcium. Breads made from theseconventional flours will obviously contain only a small fraction of therecommended daily calcium intake.

It is conventional in the baking industry to add sources of calcium tobread products as “dough conditioners.” Typically, calcium sulfate orcalcium carbonate is added to dough in order to regulate pH and increasethe electrolytic strength of soft water to prevent soft or sticky dough.Such calcium dough conditioners are usually added to dough from about0.1 to 0.6% by weight. These calcium dough conditioners are not presentin sufficient amounts to contribute significantly to the calcium valueof the resulting bread products.

Calcium sulfate and calcium carbonate cannot be added directly to doughin sufficiently large amounts to contribute to the calcium content ofbread due to inherent limitations imposed by the chemistry of the dough.In the fermentation process that occurs in leavened breads, pH plays acritical role in controlling yeast activity, amylolytic activity, andgluten behavior. The pH of bread typically ranges from about 5.1 toabout 5.4. To reach these final pH levels, the dough must have final pHlevel as low as 4.5 to 5.2, however the pH must drop even lower duringthe fermentation process.

For example, in the typical commercial production of leavened bread bythe sponge-dough process, the pH of the initially mixed spongeingredients is about 5.3. As the fermentation process proceeds, the pHwill rapidly drop over the first two hours of incubation. The drop in pHis principally the result of the lactic, succinic, and acetic acidsproduced by fermentation. Over the next two hours of fermentation, thepH will stabilize to a final value of about 4.7. When the remainingdough ingredients are added to the sponge, the pH will quickly rise backto its initial value of about 5.3 due to the diluting and bufferingeffects of the added flour. Subsequent fermentation again results in pHdrop to a final value of about 5.0. As the dough is baked,volatilization of the fermentation acids causes the pH to rise to afinal value of about 5.4 in the finished bread product. Some specialtybreads such as French bread may have a pH as low as about 3.8 to 4.0,requiring even lower pH drops during the fermentation process.

Calcium salts such as calcium carbonate, calcium sulfate, and calciumcitrate exert a buffering effect on dough chemistry by reacting with theorganic acids produced during fermentation. Even relatively low levelsof these calcium salts will prevent the pH from dropping duringfermentation, interfering with the functioning of yeast and altering theflavor and texture of the resulting bread product. At higher levels,these salts can result in dough with a basic pH. Despite its lowsolubility in water, a saturated aqueous solution of calcium carbonatehas a pH between 9 and 10 at ambient temperatures. Thus, calciumcarbonate cannot be added directly to dough without upsetting the acidicpH characteristic of most bread dough. Further, the very low watersolubility of calcium carbonate can result in granular precipitates whenadded in large quantities to dough. For these reasons, it is notadequate to fortify bread products by directly adding traditionalcalcium salts to dough.

To date, efforts to increase the calcium content of bread by othermethods have met with only limited success.

U.S. Pat. No. 5,108,764 to Craig discloses the dough-up stage additionof calcium carbonate for its nutritive value in the production ofreduced fat or no-added fat crackers. The amount of added calciumcarbonate is described as “minor.”

U.S. Pat. No. 6,126,982 to Maldonado discloses bread products havingincreased calcium contents produced from flours having large amounts ofadded middlings. That patent purports to provide bread products havingup to 200% of the USRDA calcium dose per serving. However, theusefulness of the method disclosed by Maldonado is limited by therequirement of middling addition, since many commercial breads requirehighly purified flours.

U.S. Pat. No. 5,514,387 to Zimmerman, et al. discloses crackers andother baked goods providing greater than 10% of the USRDA calcium dose.The disclosed process uses emulsifier compositions such as combinationsof polysorbate 60 and sodium stearoyl lactylate to reduce hardness anddry mouthfeel caused by the addition of insoluble calcium salts such ascalcium carbonate. The fermented crackers produced by the methoddisclosed in this patent are reported to have pH values between 6.6 and8.2, far higher than the tolerable pH of a typical commercial bakedbread product.

U.S. Pat. Nos. 4,859,473 and 5,066,499 to Arciszewski et al disclose theaddition of calcium carbonate to the dough-up stage in a process forpreparing low sodium crackers and cookies. Calcium carbonate is addedfor its nutritive value in amounts up to about 10% by total weight. Theresulting pH of the disclosed baked goods, between 6.5 and 8, is higherthan the tolerable pH of most commercial baked bread products.

U.S. Pat. No. 6,210,720 to Leusner, et al. discloses lightly cookedcereal dough products fortified with at least 0.3% calcium. Thedisclosed process involves the addition of calcium carbonate having asmall average particle size and a calcium sequestering agent such asphosphate salts or citric acid to a traditional cereal dough. Thecalcium carbonate and the calcium sequestering agent are added to thedough in conjunction with a wet blend. Calcium fortification of leavenedbread products is not disclosed.

U.S. Pat. No. 5,945,144 to Hahn, et al. disclosed calcium fortifiedpasta produced by adding calcium salts such as calcium citrate to pastadough before extrusion. The methods disclosed would not be applicable toprepare highly calcium fortified leavened bread products.

U.S. Pat. No. 5,260,082 to delValle, et al. discloses a calcium citrateadditive for baked goods. The calcium citrate is prepared by reactingcitric acid with calcium hydroxide or calcium carbonate in aqueoussolution followed by spray drying to produce fine calcium citratecrystals. The calcium citrate crystals are added directly to the spongeto produce bread products alleged to have improved volume, shelf-life,and microwavability as compared to both control breads not having theadditive and bread products prepared from commercially available calciumcitrate. U.S. Pat. No. 5,260,082 does not disclose addition of calciumcitrate to bread products for its nutritional value.

It would be desirable to enrich a variety of bread products with calciumin sufficient quantities to supply the recommended daily calcium dose.To this end, it would be desirable to enrich bread with calciumcarbonate, since calcium carbonate is the most abundant andcost-efficient source of elemental calcium.

It is therefore an object of the present invention to provide breadproducts fortified with calcium, particularly in the form of calciumcarbonate.

It is a further object of the present invention to providecalcium-fortified bread products having organoleptic properties, crumbstructure, volume, and mouthfeel comparable to conventional breads.

It is a further object of the invention to provide calcium additives andmethods for fortifying bread products with calcium additives.

SUMMARY OF INVENTION

In accordance with the foregoing objectives, the present inventionprovides baked products, such as bread products, that are highlyfortified with calcium. Calcium additives and methods for preparing suchcalcium-fortified bread products are also provided.

It has surprisingly been found that suspensions of calcium carbonate inacidic aqueous solutions prepared under the conditions disclosed hereincan be added to dough to increase calcium content without adverselyaffecting the properties of the dough. Without wishing to be bound byany theory, it is believed that the additives of the present inventionexist as a fine suspension of calcium carbonate powder in an acidicenvironment provided by soluble inorganic or organic acids. This isunexpected as it is known that completely water-solubilized calciumcarbonate reacts with acids to form calcium salts, carbon dioxide, andwater. Such a reaction is evidenced by the evolution of carbon dioxidebubbles in appropriately prepared solutions of these ingredients. Theremoval of carbon dioxide in this manner would be expected to drive thereaction to completion. That is, insoluble calcium carbonate, which isin equilibrium with soluble calcium carbonate, would eventually beconsumed in the presence of a stoichiometric amount of acid. Theresulting solution of calcium salts would only be slightly less basicthan calcium carbonate, but still above the pH of most dough.

When calcium additives are prepared according to the present invention,however, at ambient temperatures, there is only an initial vigorousevolution of gas, which dissipates after several minutes. The initialvigorous evolution of gas is typically characterized by foaming abovethe surface of the aqueous solution indicating that some amount ofcalcium carbonate has reacted with acid. After the initial reactionsubsides, typically after about 30 seconds to about five minutes, only asmall amount of evolved gas is observed and the majority of calciumcarbonate remains as a suspension in water. Upon dissipation of initialfoaming, the pH of the solution begins to stabilize. The residualevolution of gas is characterized by visible bubbling at the surface ofthe aqueous solution and typically diminishes in intensity over the nextfive to ten minutes. After the dissipation of foaming, the pH of thesolution remains relatively stable for several minutes and possibly anhour or more. The relative stability of the pH and the dissipation offoaming after the initial reaction indicates that the compositions ofthe invention comprise relatively stable calcium carbonate suspensionsthat undergo reaction with the acid at only a slow rate. It will benoted, however, that the formation of calcium salts in low to moderateamounts is not deleterious to the practice of the invention as long asthe pH of the solution remains sufficiently acidic such that theproperties of dough will not be adversely effected upon addition of thecalcium additive.

The calcium additives of the invention are highly manageable on anindustrial scale and can be conveniently transferred to a dough mixer bytubing and the like. By the methods of the invention, the skilledartisan can select the proportions of reagents and reaction times toproduce a calcium carbonate suspension having a pH that corresponds tothe pH of any desired dough.

One aspect of the invention provides calcium additives for bread doughcomprising an aqueous solution of an inorganic or an organic acid andcalcium carbonate powder suspended in the aqueous solution of aninorganic or organic acid. The weight ratio of calcium carbonate to acidis from about 4:1 to about 20:1 and the weight ratio of water to thecombined weight of calcium carbonate and acid is from about 1:1 to about10:1. The pH of the aqueous solution is from about 3 to about 6.5. Thepreferred acid according to this aspect of the invention is citric acid.

Another aspect of the invention provides a method for preparing acalcium additive for dough comprising the steps of: (a) providing anaqueous solution of an inorganic or an organic acid; (b) providingcalcium carbonate powder suspended in the aqueous solution of aninorganic or organic acid; (c) mixing the resulting suspension ofcalcium carbonate in an aqueous solution of an inorganic or an organicacid at a mixer speed sufficiently high to maintain a substantiallyhomogenous suspension of calcium carbonate powder in the acidic aqueoussolution; and (d) allowing the aqueous solution to reach a pH of about 3to about 6.5. The weight ratio of calcium carbonate to acid is fromabout 4:1 to about 20:1 and the weight ratio of water to the combinedweight of calcium carbonate and acid is from about 1:1 to about 10:1. Inthe preferred practice of this aspect of the invention the acid is anorganic acid, and more preferably the acid is citric acid. The calciumcarbonate is preferably provided as a powder having a small meanparticle diameter.

Yet another aspect of the invention provides a method of fortifyingdough with calcium. The method according to this aspect of the inventioncomprises the steps of: (a) providing a calcium additive comprising (i)an aqueous solution of an inorganic or an organic acid and (ii) calciumcarbonate powder suspended in the aqueous solution of an inorganic ororganic acid; wherein the weight ratio of calcium carbonate to acid isfrom about 4:1 to about 20:1 and the weight ratio of water to thecombined weight of calcium carbonate and acid is from about 1:1 to about10:1; and wherein the pH of the aqueous solution is about 3 to about6.5; and (b) incorporating the calcium additive into a dough. In thepreferred practice of this aspect of the invention the acid is anorganic acid, and more preferably the acid is citric acid. Calciumfortified dough prepared in accordance with the methods of this aspectof the invention is also provided.

Another aspect of the invention provides a method of fortifying ahamburger bun with calcium comprising the steps of: (a) providing acalcium additive comprising (i) an aqueous solution of citric acid and(ii) calcium carbonate powder suspended in the aqueous solution ofcitric acid; wherein the weight ratio of calcium carbonate to citricacid is from about 4:1 to about 20:1 and the weight ratio of water tothe combined weight of calcium carbonate and citric acid is from about1:1 to about 10:1; and wherein the pH of the aqueous solution is about 3to about 6.5; and (b) providing a hamburger bun dough comprising wheatflour, preferably patent flour; and (c) incorporating the calciumadditive into the hamburger bun dough in a quantity sufficient toprovide a hamburger bun upon baking having an elemental calcium contentfrom about 0.1% to about 2.2% by weight of the hamburger bun.

A further aspect of the invention provides calcium fortified breadproducts comprising calcium from about 0.1% to about 2.2% by weight. Thebread products according to this aspect of the invention preferablycomprise flour that is substantially free of bran and/or wheatmiddlings. The pH of the bread is preferably from about 3.0 to about6.5.

These and other aspects of the invention may be more clearly understoodby reference to the following detailed description of the invention andthe appended claims.

DETAILED DESCRIPTION OF THE INVENTION

In the following description of the invention, it is to be understoodthat the terms used have their ordinary and accustomed meanings in theart, unless otherwise specified. All weights referred to herein aregiven in terms of “% by weight” of the total composition, unlessotherwise indicated. The term “% by flour weight” indicates that theingredient is measured as a percentage of the total weight of flouralone. The term “elemental calcium” refers to the element calcium in anyoxidation state, including Ca⁺². Accordingly, when the “weight” ofelemental calcium is referred to herein, that phrase refers to theweight of the element calcium, whether the calcium is in the form of asalt or otherwise.

The calcium additives for bread dough according to one embodiment of theinvention comprise an aqueous solution of an inorganic or an organicacid and calcium carbonate powder suspended in the aqueous solution ofan inorganic or organic acid. The weight ratio of calcium carbonate toacid is from about 4:1 to about 20:1 and the weight ratio of water tothe combined weight of calcium carbonate and acid is from about 1:1 toabout 10:1. The pH of the aqueous solution is from about 3 to about 6.5.The calcium additive according to this aspect of the invention compriseswater in a weight ratio from about 1:1 to about 5:1 in one embodimentand from about 1:1 to about 3:1 in another embodiment. The mostpreferred calcium additives comprises water in a weight ratio of about1.8:1 based on the combined weight of the calcium carbonate and acid. Ina preferred embodiment, the ratio of calcium carbonate to acid in thecalcium additive ranges from about 7:1 to about 15:1 by weight, and morepreferably, about 11:1. Preferred calcium additives have a pH of about4.0 to about 6.5 and more preferably from about 4.5 to about 5.6.

Any acid compatible with food products may be used in the practice ofthe invention. The acid may be either an organic or an inorganic acid.Useful inorganic acids include but are not limited to phosphoric acidand sulfuric acid. More preferred acids according to the invention areorganic acids, and more preferably, organic carboxylic acids.Appropriate organic acids include but are not limited to formic acid,acetic acid, ethanolic acid, adipic acid, citric acid, tartaric acid,glutaric acid, lactic acid, oxalic acid, ascorbic acid, glycolic acid,mevalonic acid, malic acid, tartronic acid, maleic acid, fumaric acid,malonic acid and succinic acid. Presently preferred carboxylic acids foruse herein include citric acid, fumaric acid, lactic acid, and malicacid. An especially preferred acid is citric acid.

In the preferred practice of the invention, calcium carbonate isprovided as a powder having a small mean particle diameter. In oneembodiment, calcium carbonate is provided as a powder having a meanparticle diameter from about 0.05 μm to about 30 μm. Preferably, themean particle diameter of the calcium carbonate powder is from about 1μm to about 25 μm, more preferably from about 5 μm to about 20 μm, andmost preferably from about 10 μ to about 15 μm. As used herein, thesymbol “μm” refers to micrometers.

It is well known in the art that calcium carbonate powders having avariety of median particle diameters are commercially available. Forexample, food grade and USP grade calcium carbonate powders havingmedian particle diameters ranging from 0.7 to 20 μm are available fromsuppliers such as OMYA, Inc. (Alpharetta, Ga.), J.M Huber Corp.(Atlanta, Ga.), and Minerals Technologies Inc. (New York, N.Y.).Suitable calcium carbonate powders include but are not limited to thoseavailable from OMYA, Inc. under the trademarks OMYA-Cal FG 15, OMYA-CalUSP 15, OMYA-Cal LL OC FG 15 BTH, OMYA-Cal LL USP 15, OMYA-Cal LL USP 15BTH, OMYA-Cal FG-10AZ, OMYA-Cal FG-6AZ, and OMYA-Cal USP-4AZ.

While the calcium additives according to this embodiment of theinvention are preferably employed to enrich the calcium content of bakedgoods, particularly leavened breads, it is contemplated that theseadditives will also be useful for enriching the calcium content of avariety of food products.

In another embodiment of the invention, a method for preparing a calciumadditive for dough is provided. This method comprises the steps of: (a)providing an aqueous solution of an inorganic or an organic acid; (b)providing calcium carbonate powder suspended in the aqueous solution ofan inorganic or organic acid; wherein the weight ratio of calciumcarbonate to acid is from about 4:1 to about 20:1 and the weight ratioof water to the combined weight of calcium carbonate and acid is fromabout 1:1 to about 10:1; (c) mixing the resulting suspension of calciumcarbonate in an aqueous solution of an inorganic or an organic acid at amixer speed sufficiently high to maintain the calcium carbonate powderas a substantially homogenous suspension in the aqueous solution; and(d) allowing the aqueous solution to reach a pH of about 3 to about 6.5.The calcium carbonate is preferably provided as a powder having a smallmean particle diameter as described above. In a preferred embodiment,the ratio of calcium carbonate to acid, preferably citric acid, in thecalcium additive ranges from about 7:1 to about 15:1 by weight, and morepreferably about 11:1. In one embodiment, the weight ratio of water tothe combined weight of calcium carbonate and acid is from about 1:1 toabout 5:1. In another embodiment, the weight ratio of water to thecombined weight of calcium carbonate and acid is from about 1:1 to about3:1. Preferred calcium additives comprise water in a weight ratio ofabout 1.8:1 based on the combined weight of the calcium carbonate andacid. Preferred calcium additives have a pH of about 4.0 to about 6.5and more preferably from about 4.5 to about 5.6.

Any mixing vessel may be used to combine the water, calcium carbonate,and citric acid. Preferably, the mixing vessel is the mixing bowl of amechanical mixer such as a Hobart mixer. However, it is contemplatedthat the water, calcium carbonate, and citric acid may first be combinedin one vessel and subsequently transferred to the mixing bowl of asuitable mixer. The calcium carbonate, citric acid, and water may beadded in any order or added simultaneously to the mixing vessel.Preferably, the mixing vessel is first charged with water. It has beenfound desirable to employ a mixing vessel that is approximately twicethe volume of added water or more since the initial vigorous reactionmay result in foaming or vigorous bubbling which increases the totalvolume of material in the mixing bowl by up to 100%. It is contemplatedthat various anti-foaming agents such as silicone may be useful in thepractice of the invention to mitigate the effects of foaming.

Any mixer that provides sufficient agitation to maintain the calciumcarbonate as a substantially homogenous suspension in the aqueoussolution may be used in the practice of the invention. Preferably, themixer is a high speed mixer. As used herein, the phrase “high speedmixing” refers to mixing speeds capable of creating a deep vortex. Atlow agitation rates, the calcium carbonate may precipitate or settle outof the aqueous solution, resulting in a substantially non-homogenoussuspension. It is within the knowledge of the skilled artisan to selectan appropriate mixer and mixing conditions.

Upon addition of the ingredients and initiation of high speed mixing, aninitial vigorous evolution of gas is observed. In the absence ofanti-foaming agents, the initial reaction typically produces a foam,which increases the volume of the mixture from about 10% to about 100%.Depending on the selection of acid, the foam typically dissipates afterabout one or two minutes and yields to moderate to vigorous bubbling.The moderate to vigorous bubbling subsides after several minutes,typically about 4 to about 10 minutes. After about 4 to about 10minutes, only a small amount of evolved gas is observed and the majorityof calcium carbonate remains as a suspension in water. The duration ofthe initial vigorous production of carbon dioxide bubbles will dependupon a variety of factors such as, for example, temperature, mixingspeed, mean particle diameter of calcium carbonate, volume of waterutilized, selection of acid, and the ratio of calcium carbonate to acid.It is within the skill in the art to modify these and other parametersto control the duration of the initial vigorous evolution of gas.Typically, after about 4 to 10 minutes, the mixer speed is preferablylowered. The mixer speed is preferably adjusted to maintain the mixtureas a substantially homogenous suspension. It will be understood that thereduction in mixer speed is merely a matter of convenience, as it hasbeen found easier to manipulate the suspension at lower mixing speeds.That is, it has been found to be advantageous to transfer the calciumadditive through tubing and the like at lower agitation rates. The pH ofthe solution remains relatively stable for several minutes, typicallyten minutes, and possibly an hour or more. The skilled artisan canadjust the time of the reaction and the mixing speed to achieve amixture having a desired pH.

In another embodiment of the invention a method of fortifying dough withcalcium is provided. The method according to this embodiment of theinvention comprises the steps of: (a) providing a calcium additivecomprising (i) an aqueous solution of an inorganic or an organic acidand (ii) calcium carbonate powder suspended in the aqueous solution ofan inorganic or organic acid; wherein the weight ratio of calciumcarbonate to acid is from about 4:1 to about 20:1 and the weight ratioof water to the combined weight of calcium carbonate and acid is fromabout 1:1 to about 10:1; and wherein the pH of the aqueous solution isabout 3 to about 6.5; and (b) incorporating the calcium additive into adough. In a preferred embodiment, the ratio of calcium carbonate toacid, preferably citric acid, in the calcium additive ranges from about7:1 to about 15:1 by weight, and more preferably about 11:1. In oneembodiment, the weight ratio of water to the combined weight of calciumcarbonate and acid is from about 1:1 to about 5:1. In anotherembodiment, the weight ratio of water to the combined weight of calciumcarbonate and acid is from about 1:1 to about 3:1. Preferred calciumadditives comprise water in a weight of about 1.8:1 based on thecombined weight of the calcium carbonate and acid. Preferred calciumadditives have a pH of about 4.0 to about 6.5 and more preferably fromabout 4.5 to about 5.6. In the preferred practice of this aspect of theinvention, the calcium carbonate, citric acid and water are mixed forabout 5 to about 10 minutes prior to addition to dough. The exact timeof mixing may vary depending on factors such as the quantity ofmaterials and the mixing speed. Preferably, the solution should be mixedlong enough for the evolution of gas to substantially subside, but notso long that the solution develops a basic pH.

The calcium additives may be added to dough ingredients in any manner.For example, the calcium additives may be poured directly into themixing bowl containing the dough ingredients. Alternatively, the calciumadditives may be pumped into the mixing bowl containing the doughingredients through tubing and the like. It is anticipated that thecalcium additives of the invention will be well suited to large,industrial scale applications such as those used in commercial bakeries.

The calcium additives may be added to any type of dough. Preferably, thedough comprises a leavening agent. It is contemplated that the dough maycomprise any leavening agent known in the art including but not limitedto chemical leavening agents and bacterial leavening agents. In thepreferred practice of the invention, the leavening agent is yeast.

The calcium additives are preferably added to dough from about 2 toabout 10% by weight based on the weight of dough. More preferably, thecalcium additives are added from about 4 to about 6% by weight based onthe weight of dough. In the most preferred practice of the invention,the calcium additives are added from about 5 to about 6% by weight basedon the weight of dough.

The calcium additives may be employed in any of the known methods forpreparing bread dough, including but not limited to the “straight dough”method, the “sponge dough” method, the “continuous mixing” method, the“liquid sponge” method, the “liquid ferment” method, and the “no-timedough” method. The sponge dough method is the preferred method employedin commercial bakeries.

In the sponge dough method, a quantity of dough, called a “sponge,” isprepared which serves as a pre-ferment. The sponge is combined with thebalance of bread ingredients at a later stage. In a typical process, thesponge is formed by mixing over half of the flour, most if not all ofthe yeast, and a quantity of water sufficient to stiffen the dough, forabout four minutes in a conventional dough mixer. The sponge is then setto ferment for about three to five hours depending on the amount offlour incorporated into the sponge. The fermented sponge is the mixedwith the balance of ingredients in a dough mixer. The resulting dough isthen set to ferment for an additional period from about fifteen minutesto one hour before baking. It will be understood that this procedure ismerely representative and any variations and modifications of thismethod are contemplated to be with in the skill of the ordinary artisan

In a sponge dough method, as with any method involving a pre-fermentstage, the calcium additive is preferably added to the dough rather thanto the sponge. However, it is contemplated that the calcium additive maybe added to the sponge before the remaining flour is combined with thesponge. Further, portions of the calcium additive may be added to boththe sponge and the final dough. If a liquid ferment method is employed,it is preferable to add the calcium additive during the dough mixingstage after the ferment has been added.

In one embodiment, the final pH of the dough is from about 3.0 to about6.0. In another embodiment, the final pH of the dough is from about 4.0to about 5.8. In yet another embodiment, the final pH of the dough isfrom about 5.0 to about 5.4.

It will be understood that the optimal weight ratio of calcium carbonateto citric acid may vary within the suitable ranges based on the pH ofthe dough to which it is added. For example, it is not uncommon for somedoughs, such as, for example, sourdough, to attain pH levels of 3.5 orlower during fermentation. With such highly acidic dough it is possibleto adjust the ratio of calcium carbonate to acid toward the upper end ofthe suitable range, i.e., from about 15:1 to about 20:1. It will beevident to the skilled artisan to adjust the ratio in accordance withthe desired pH of the dough.

The dough may contain any type of flour. Preferred flours are thosetraditionally used to prepare bread products. The most preferred floursaccording to the invention are those used to prepare white breads, buns,and rolls, such as patent flour and clear patent flour.

The term “flour” as used herein includes, but is not limited to patentflour, all-purpose flour, bleached flour, bread flour, cake flour,cookie flour, cracker flour, durum flour, enriched flour, farina, grahamflour, pastry flour, rice flour, rye flour, self-rising flour, semolina,unbleached flour, wheat flour, whole-wheat flour, wheat meal, corn meal,corn flour, durum flour, rye meal, rye flour, oat meal, oat flour, soymeal, soy flour, sorghum meal, sorghum flour, potato meal, and potatoflour.

Preferred flours for use in the present invention are patent flour,clear patent flour, all-purpose flour, farina flour, and bleached flour.The most preferred flours are those conventionally used to preparedwhite breads, buns, and rolls. Most preferred flours according to theinvention have gluten contents from about 6 to about 14% by weight. Inone embodiment of the invention, these preferred flours comprise 100% byweight of the total flour content of the dough. In other embodiments,the preferred flours comprise 99, 98, 97, 96, 95, 94, 93, 92, 91 or 90%by weight of the total flour content of the dough.

In one embodiment of the invention the dough comprises flour that issubstantially free of wheat middlings. As used herein, flour that is“substantially free of wheat middlings” contains less than about 5% byweight wheat middlings. In another embodiment of the invention the doughcomprises flour that is substantially free of bran. As used herein,flour that is “substantially free of bran” contains less than about 5%by weight bran.

While the foregoing description relates to dough made from flour, theinvention is not so limited. It will be understood that the dough of thepresent invention may be prepared from flour alternatives. “Bread-type”products that do not comprise flour or are substantially free of flourmay be prepared according to the present invention. Such bread-typeproducts may be prepared from flour-free dough comprising, for example,gluten and grain. A bread-type product that is “substantially free” offlour will have a flour content of less than about 10% by weight basedon total dry ingredients, and preferably will have a flour content ofless than about 5% by weight based on total dry ingredients.

In addition to flour, the dough may contain any ingredients known in theart for use in bread products, including but not limited to salt, fatand oil, sugar, shortening, butter, milk, dry milk, yeast food, eggs,and vegetable gums.

Calcium fortified dough prepared in accordance with the methods of thisaspect of the invention is also provided. The dough may be any type ofdough known in the art, including but not limited to bread dough, bageldough, pasta dough, cereal dough, cracker dough, cookie dough, cakedough, pastry dough, and pizza dough.

A further aspect of the invention provides calcium fortified bakedproducts comprising calcium from about 0.1% to about 2.2% by weight. Inone embodiment, the calcium fortified baked products comprise calciumfrom about 0.5% to about 1.8% by weight. In another embodiment, thecalcium fortified baked products comprise calcium from about 0.8% toabout 1.2% by weight. In still another embodiment, the calcium fortifiedbaked products comprise calcium from about 0.9% to about 1.2% by weight.In yet another embodiment, the calcium fortified baked products comprisecalcium from about 1.0% to about 1.2% by weight. It will be understoodthat the phrase “comprising calcium from about 0.2% to about 1.2% byweight” refers to the weight of elemental calcium rather than the weightof a calcium salt.

The baked products according to this aspect of the invention preferablycomprise flour that is substantially free of bran and/or wheatmiddlings. Preferably, the baked products comprise patent flour.

In one embodiment, the pH of the calcium fortified baked product is fromabout 3.0 to about 6.0. In another embodiment the pH of the calciumfortified baked product is from about 4.0 to about 5.8. In yet anotherembodiment, the pH of the calcium fortified baked product is from about5.0 to about 5.4.

The baked products according to this aspect of the invention arepreferably bread products. The baked products according to this aspectof the invention may be leavened or unleavened bread products. Theadditives and methods disclosed herein are particularly useful in thepreparation of leavened bread products.

Baked products according to the invention include, but are not limitedto, white bread, wheat bread, tortillas, rolls and buns,specialty/artisan breads, rye bread, whole grain varietals, bagels,pasta, grain-based snack foods, cereals, crackers, cookies, cakes,muffins, pastries, pancakes, pizza crusts, doughnuts, danishes,grain-based nutritional supplements, and salty snacks such as pretzels,tortilla chips, corn chips, and potato chips.

The baked products provided by the present invention have a texture,crumb structure, taste, and “mouth feel” substantially identical tobaked products that do not have added calcium. The baked products do nothave a “grainy” texture that is characteristic of high levels ofinsoluble calcium carbonate.

The preferred bread products according to the invention are hamburgerbuns. Accordingly, a preferred embodiment of the invention is a methodof fortifying a hamburger bun with calcium. The method comprises thesteps of: (a) providing a calcium additive comprising (i) an aqueoussolution of citric acid and (ii) calcium carbonate powder suspended inthe aqueous solution of citric acid; wherein the weight ratio of calciumcarbonate to citric acid is from about 4:1 to about 20:1 and the weightratio of water to the combined weight of calcium carbonate and citricacid is from about 1:1 to about 10:1; and wherein the pH of the aqueoussolution is about 3 to about 6.5; (b) providing a hamburger bun doughcomprising wheat flour, preferably patent flour; and (c) incorporatingthe calcium additive into the hamburger bun dough. The weight ratio ofcalcium carbonate to citric acid from about 7:1 to about 15:1, morepreferably from about 9:1 to about 13:1, are particularly useful rangesaccording to this embodiment. With respect to hamburger buns and otherbread products having similar pH, the currently preferred weight ratioof calcium carbonate to citric acid is about 11:1.

In one embodiment, the weight ratio of water to the combined weight ofcalcium carbonate and citric acid in the calcium additive is from about1:1 to about 5:1. In another embodiment, the weight ratio of water tothe combined weight of calcium carbonate and citric acid is from about1:1 to about 3:1. Preferred calcium additives according to thisembodiment comprise water in a weight ratio of about 1.8:1 based on thecombined weight of the calcium carbonate and citric acid.

Hamburger bun dough prepared according the invention will preferablycomprise wheat flour. In a preferred embodiment, the wheat flour ispatent flour. The wheat flour preferably will comprise about 99, 98, 97,96, 95, 94, 93, 92, 91 or 90% by weight of the total flour content ofthe hamburger bun dough. While patent flour is the preferred flouraccording to this aspect of the invention, other highly purified flourssuch as clear patent flour may be substituted for patent flour. Thecalcium additive is incorporated into the hamburger bun dough in aquantity sufficient to provide a hamburger bun upon baking having anelemental calcium content from about 0.1% to about 2.2% by weight of thehamburger bun. In another embodiment, the hamburger bun upon baking hasan elemental calcium content from about 0.8% to about 1.8% by weight ofthe hamburger bun. In yet another embodiment, the hamburger bun uponbaking has an elemental calcium content from about 0.9% to about 1.2% byweight of the hamburger bun. In a further embodiment, the hamburger bunupon baking has an elemental calcium content from about 1.0% to about1.2% by weight of the hamburger bun. The calcium carbonate powder ispreferably one having a small mean particle diameter. Preferred calciumcarbonate powders have mean particle diameters of about 0.05 μm to about30 μm, more preferably from about 1 μm to about 25 μm, and even morepreferably from about 5 μm to about 20 μm. The most preferred calciumcarbonate powders according to this embodiment have mean particlediameters from about 10 μm to about 15 μm.

It will be understood that the recitation of certain ranges hereinshould not be construed to limit the disclosure to the endpointsdisclosed. For example, the range “3.0 to 6.0” will be understood todisclose every value in between and is equivalent to the disclosure“3.0, 4.0, 5.0, and 6.0” or “3.0, 3.1, 3.2, 3.3 . . . 5.7, 5.8, 5.9, and6.0.” The intermediate values within each recited range are explicitlyor inherently disclosed by the disclosure of the broader range.Similarly, the disclosure of a range will be understood to inherentlydisclose more narrow ranges therein. The phrase “about” is intended tomodify every value within the range.

EXAMPLE 1

This example illustrates the use of various inorganic and organic acidsin the practice of the invention. In each of the following experiments,25 g of calcium carbonate powder (OMYA Cal Carb LL FG 15 PDR) wassuspended in 60 ml of deionized water in a 150 ml graduated glass beakerequipped with a Teflon coated magnetic stir bar. The stirring speed wasadjusted to provide a deep vortex. 5 g of acid was then added to thesuspension and the pH of the aqueous phase was measured every minuteusing an Orion 420A+ pH meter. Table I provides the pH of each solutionfor a 10 minute period following addition of the acid to the solution.TABLE I The pH of Calcium Carbonate Suspensions in Various Acids TimeCitric Fumaric Lactic Malic Phosphoric (minutes) pH pH pH pH pH 0 3.325.10 2.82 3.28 3.11 1 4.00 5.32 5.32 4.08 4.36 2 4.29 5.21 5.30 4.445.42 3 4.45 5.25 5.31 4.65 5.54 4 4.58 5.31 5.35 4.82 5.58 5 4.68 5.325.39 4.92 5.59 6 4.76 5.41 5.42 5.00 5.59 7 4.82 5.48 5.43 5.07 5.61 84.88 5.47 5.44 5.12 5.62 9 4.92 5.47 5.44 5.16 5.63 10 4.95 5.47 5.445.20 5.65

In each case, it can be seen that after an initially rapid increase inpH following the addition of each acid, the pH becomes relatively stableunder these conditions. For example, the pH increase from the second tothe tenth minute ranges from 0.14 for lactic acid to 0.76 for malicacid. It is clear from the data in Table II that calcium carbonateinitially reacts with each acid to form some amount of calcium salt asevidenced by the rapid rise in pH. After approximately one or twominutes, however, the reaction slows and the pH of the aqueoussuspensions of calcium carbonate becomes relatively stable under theseconditions. In each case, the solution remains acidic after 10 minutesand is therefore suitable for addition to bread dough, particularlybread dough comprising a leavening agent.

In each case, vigorous bubbling was observed following the addition ofthe acid. The vigorous bubbling was evidenced by foaming which resultedin an increase in the total volume of the material in the beaker. Thatis, the surface of the solution was no longer visible due to thepresence of foam above the surface.

In the case of citric acid, foaming lasted for approximately one minuteafter addition of the acid. The total volume in the beaker increased byapproximately 12% during this time. After about 2 minutes, the foam haddissipated and the volume in the beaker returned to the initial value.After five minutes, there was almost no bubbling and the surface of theliquid was entirely visible

When fumaric acid was added to an aqueous calcium carbonate suspension,the results were similar to those seen with citric acid. Initial foamingwhich resulted in an increase in the total volume in the beaker of about12% subsided after about four minutes. After five minutes, the surfaceof the solution was entirely visible and only moderate bubbling wasobserved.

In the case of lactic acid, foaming increased the volume in the beakerby about 75% after addition of the acid. After about two minutes, thefoam had settled to about 12% above the initial volume of the solutionand held relatively constant until about four minutes after addition ofthe acid. After about eight minutes, the foaming had substantiallydissipated and bubbling became visible on the surface of the solution.

When malic acid was added to an aqueous suspension of calcium carbonate,foaming lasted for approximately 20 seconds and increased the volume inthe beaker by about 38%. After one minute, the foaming had largelydissipated an the volume in the beaker was about 12% greater than itsinitial value. After two minutes, the volume had returned to its initialvalue and no foaming was present. Bubbling was visible on the surface ofthe solution after two minutes, gradually decreasing in magnitude untilonly minimal bubbling was observed after eight minutes.

Phosphoric acid behaved similarly to the organic acids; however, theinitial foaming was more substantial, resulting in a 100% increase inthe volume of material in the beaker after about ten seconds as a resultof vigorous foaming. After about 30 seconds to one minute, the foamingsubsided resulting in a suspension having a volume about 12% greaterthan the initial value. After about four minutes, the surface of theliquid was visible and very little bubbling was observed.

EXAMPLE 2

This example provides a calcium additive according to the invention. 30L of water was added to the mixing bowl of a Hobart mixer. The mixingbowl was 18 inches in diameter having 36-inch straight sides with aconical bottom and a volume of 60 L. To the water was added 12,106 g ofcalcium carbonate powder (OMYA Cal Carb LL OC FG 15) having a medianparticle diameter of 15 μm and 2,422 g of citric acid. The ingredientswere mixed for 5 minutes at a “high” mixer speed. The mixer speed wasselected so as to form a deep vortex. In the case of the Hobart mixeremployed, a mixer speed of 1,440 rotations per minute was found to beadequate to provide a deep vortex. Initial foaming lasted for about oneto two minutes and subsequently gave way to bubbling which subsidedafter approximately four to five minutes. After approximately fiveminutes, the mixer speed was lowered to approximately 720 rotations perminute and the pH of the solution was measured using an STD pH meter.The pH of solution was approximately 5. After an additional 5 minutes,the pH of the solution was measured again and found to be approximately4.8. The calcium additive had the consistency of a uniform aqueoussuspension of fine calcium carbonate powder.

EXAMPLE 3

This Example provides a calcium-fortified white bread made using thecalcium additive of Example 2. The bread was made with the sponge anddough technique using the ingredients listed in Table II. In thisExample, the calcium additive was added to the dough rather than thesponge. TABLE II % by Flour % by Ingredient Sponge¹ Dough Total WeightWeight Flour² 700.00 300.00 1000.00 100.00 53.46% Water 437.00 117.00554.00 55.40 29.62% HFCS³ 182.00 182.00 18.20 9.73% Yeast⁴ 14.00 6.0020.00 2.00 1.07% Vegetable Oil⁵ 12.54 37.00 49.54 4.95 2.65% Salt⁶ 2.5017.50 20.00 2.00 1.07% SSL⁷ 3.00 0.00 3.00 0.30 0.16% Datem⁸ 1.00 1.000.10 0.05% Emulsifier⁹ 5.00 5.00 0.50 0.27% Calcium Additive¹⁰ 31.0031.00 3.10 1.66% Calcium 1.10 1.10 0.11 0.06% Propionate¹¹ Gluten¹² 4.004.00 0.40 0.21%¹All weights are provided in grams;²patent flour from ADM;³high fructose corn syrup from A E Staley;⁴Fleischmann's;⁵soy oil from Riceland Foods;⁶US Salt;⁷stearoyl-2-lactylate sold under the name Emplex by AmericanIngredients;⁸diacetyl tartaric acid esters of monoglycerides sold under the namePanodan by Danisco;⁹Max Soft 90 from American Ingredients;¹⁰the calcium additive composition described in Example 2;¹¹Fleischmann's;¹²vital wheat gluten from Manildra.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The sources ofeach ingredient listed in Table II are the same throughout the Examplesthat follow. The resulting bread contained 330 mg of elemental calciumfor each 60 g serving size. The bread had a texture, crumb structure,taste, and “mouth feel” substantially identical to white bread.

EXAMPLE 4

This Example provides another calcium-fortified white bread made usingthe calcium additive of Example 2. The bread was made with the spongeand dough technique using the ingredients listed in Table III. In thisExample, the calcium additive was added to the sponge. TABLE III % byFlour % by Ingredient Sponge¹ Dough Total Weight Weight Flour 700.00300.00 1000.00 100.00 53.46% Water 437.00 117.00 554.00 55.40 29.62%HFCS 182.00 182.00 18.20 9.73% Yeast 14.00 6.00 20.00 2.00 1.07%Vegetable Oil 12.54 37.00 49.54 4.95 2.65% Salt 2.50 17.50 20.00 2.001.07% SSL 3.00 0.00 3.00 0.30 0.16% Datem 1.00 1.00 0.10 0.05%Emulsifier 5.00 5.00 0.50 0.27% Calcium Additive² 31.00 0.00 31.00 3.101.66% Calcium Propionate 1.10 1.10 0.11 0.06% Gluten 4.00 4.00 0.400.21%¹All weights are provided in grams.²The calcium additive composition described in Example 2.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The resultingbread contained 330 mg of elemental calcium for each 60 g serving size.The bread had a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

EXAMPLE 5

This Example provides a calcium-fortified white bread made using thecalcium additive of Example 2. The bread was made with the straightdough technique using the ingredients listed in Table IV. In thisExample, all of the ingredients, including the calcium additive, werecombined to form the dough. TABLE IV % by Flour Ingredient Total Weight% by Weight Flour 1000.00 100.00 53.46% Water 554.00 55.40 29.62% HFCS182.00 18.20 9.73% Yeast 20.00 2.00 1.07% Vegetable Oil 49.54 4.95 2.65%Salt 20.00 2.00 1.07% SSL 3.00 0.30 0.16% Datem 1.00 0.10 0.05%Emulsifier 5.00 0.50 0.27% Calcium Additive² 31.00 3.10 1.66% CalciumPropionate 1.10 0.11 0.06% Gluten 4.00 0.40 0.21%¹All weights are provided in grams.²The calcium additive composition described in Example 2.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The resultingbread contained 330 mg of elemental calcium for each 60 g serving size.The bread had a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

EXAMPLE 6

This Example provides a calcium-fortified white bread made using thecaclium additive of Example 2. The bread was made with the no-time doughtechnique using the ingredients listed in Table V. TABLE V % by FlourIngredient Total Weight % by Weight Flour 1200.00 100.00 54.23% Water613.00 51.08 27.70% HFCS 219.00 18.25 9.90% Yeast 47.00 3.92 2.12% Veg.Oil 47.00 3.92 2.12% Salt 22.00 1.83 0.99% SSL 3.50 0.29 0.16% Datem1.20 0.10 0.05% Emulsifier 12.00 1.00 0.54% L-Cysteine 4.00 0.33 0.18%Calcium Additive² 36.50 3.04 1.65% Calcium Propionate 1.40 0.12 0.06%Gluten 6.00 0.50 0.27%¹All weights are provided in grams.²The calcium additive composition described in Example 2.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The resultingbread contained 330 mg of elemental calcium for each 60 g serving size.The bread had a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

EXAMPLE 7

This Example provides another calcium-fortified white bread made usingthe calcium additive of Example 2. The bread was made with the “liquidsponge” technique using the ingredients listed in Table III. Thistechnique is similar to the sponge dough technique, however, themajority of the flour is added at the dough stage. In this Example, thecalcium additive was added at the dough stage. TABLE VI % by Flour % byIngredient Sponge¹ Dough Total Weight Weight Flour 506.00 694.00 1200.00100.00 54.35% Water 486.00 127.00 613.00 51.08 27.77% HFCS 219.00 219.0018.25 9.92% Yeast 29.00 18.00 47.00 3.92 2.13% Vegetable Oil 12.54 34.1146.65 3.89 2.11% Salt 5.01 16.47 21.48 1.79 0.97% SSL 3.50 3.50 0.290.16% Datem 1.20 1.20 0.10 0.05% Emulsifier 12.00 12.00 1.00 0.54%Calcium Additive² 0.00 36.50 36.50 3.04 1.65% Calcium Propionate 1.401.40 0.12 0.06% Gluten 6.00 6.00 0.50 0.27%¹All weights are provided in grams.²The calcium additive composition described in Example 2.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The resultingbread contained 330 mg of elemental calcium for each 60 g serving size.The bread had a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

The invention having been described by the forgoing description of thepreferred embodiments, it will be understood that the skilled artisanmay make modifications and variations of these embodiments withoutdeparting from the spirit or scope of the invention as set forth in thefollowing claims.

EXAMPLES 8-13

The following examples illustrate the currently preferred aspects of thepresent invention.

EXAMPLE 8

This example provides a calcium additive according to the invention. 30L of water is added to the mixing bowl of a Hobart mixer which is 18inches in diameter having 36-inch straight sides with a conical bottomand a volume of 60 L. To the water is added 13,317 g of calciumcarbonate powder (OMYA Cal Carb LL OC FG 15) having a median particlediameter of 15 μm and 1,211 g of citric acid. The ingredients are mixedas described in Example 2. The calcium additive has the consistency of auniform aqueous suspension of fine calcium carbonate powder.

EXAMPLE 9

This Example provides a calcium-fortified white bread made using thecalcium additive of Example 8. The bread is made with the sponge anddough technique using the ingredients listed in Table VII. In thisExample, the calcium additive is added to the dough rather than thesponge. TABLE VII % by Flour % by Ingredient Sponge¹ Dough Total WeightWeight Flour² 700.00 300.00 1000.00 100.00 53.53 Water 437.00 117.00554.00 55.40 29.66 HFCS³ 182.00 182.00 18.20 9.74 Yeast⁴ 14.00 6.0020.00 2.00 1.07 Vegetable Oil⁵ 12.54 37.00 49.54 4.95 2.65 Salt⁶ 2.5017.50 20.00 2.00 1.07 SSL⁷ 3.00 0.00 3.00 0.30 0.16 Datem⁸ 1.00 1.000.10 0.05 Emulsifier⁹ 5.00 5.00 0.50 0.27 Calcium Additive¹⁰ 28.50 28.502.8 1.53 Calcium 1.10 1.10 0.11 0.059 Propionate¹¹ Gluten¹² 4.00 4.000.40 0.21¹All weights are provided in grams;²patent flour from ADM;³high fructose corn syrup from A E Staley;⁴Fleischmann's;⁵soy oil from Riceland Foods;⁶US Salt;⁷stearoyl-2-lactylate sold under the name Emplex by AmericanIngredients;⁸diacetyl tartaric acid esters of monoglycerides sold under the namePanodan by Danisco;⁹Max Soft 90 from American Ingredients;¹⁰the calcium additive composition described in Example 8;¹¹Fleischmann's;¹²vital wheat gluten from Manildra.

The calcium-fortified white bread prepared in this Example is made frompatent flour having a protein content of 11% by weight. The sources ofeach ingredient listed in Table VII are the same throughout the Examplesthat follow. The resulting bread contains 330 mg of elemental calciumfor each 60 g serving size. The bread has a texture, crumb structure,taste, and “mouth feel” substantially identical to white bread.

EXAMPLE 10

This Example provides another calcium-fortified white bread made usingthe calcium additive of Example 8. The bread is made with the sponge anddough technique using the ingredients listed in Table VIII. In thisExample, the calcium additive is added to the sponge. TABLE VIII % byFlour % by Ingredient Sponge¹ Dough Total Weight Weight Flour 700.00300.00 1000.00 100.00 53.53 Water 437.00 117.00 554.00 55.40 29.66 HFCS182.00 182.00 18.20 9.74 Yeast 14.00 6.00 20.00 2.00 1.07 Vegetable Oil12.54 37.00 49.54 4.95 2.65 Salt 2.50 17.50 20.00 2.00 1.07 SSL 3.000.00 3.00 0.30 0.16 Datem 1.00 1.00 0.10 0.05 Emulsifier 5.00 5.00 0.500.27 Calcium Additive² 28.50 0 28.50 2.85 1.53 Calcium Propionate 1.101.10 0.11 0.06 Gluten 4.00 4.00 0.40 0.21¹All weights are provided in grams.²The calcium additive composition described in Example 8.

The calcium-fortified white bread prepared in this Example is made frompatent flour having a protein content of 11% by weight. The resultingbread contains 330 mg of elemental calcium for each 60 g serving size.The bread has a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

EXAMPLE 11

This Example provides a calcium-fortified white bread made using thecalcium additive of Example 8. The bread was made with the straightdough technique using the ingredients listed in Table IX. In thisExample, all of the ingredients, including the calcium additive, werecombined to form the dough. TABLE IX % by Flour Ingredient Total Weight% by Weight Flour 1000.00 100.00 53.53 Water 554.00 55.40 29.66 HFCS182.00 18.20 9.74 Yeast 20.00 2.00 1.07 Vegetable Oil 49.54 4.95 2.65Salt 20.00 2.00 1.07 SSL 3.00 0.30 0.16 Datem 1.00 0.10 0.05 Emulsifier5.00 0.50 0.27 Calcium Additive² 28.50 2.85 1.53 Calcium Propionate 1.100.11 0.06 Gluten 4.00 0.40 0.21¹All weights are provided in grams.²The calcium additive composition described in Example 8.

The calcium-fortified white bread prepared in this Example is made frompatent flour having a protein content of 11% by weight. The resultingbread contains 330 mg of elemental calcium for each 60 g serving size.The bread has a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

EXAMPLE 12

This Example provides a calcium-fortified white bread made using thecalcium additive of Example 8. The bread was made with the no-time doughtechnique using the ingredients listed in Table X. TABLE X % by FlourIngredient Total Weight % by Weight Flour 1200.00 100.00 54.31% Water613.00 51.08 27.74% HFCS 219.00 18.25 9.91% Yeast 47.00 3.92 2.13% Veg.Oil 47.00 3.92 2.13% Salt 22.00 1.83 1.0% SSL 3.50 0.29 0.16% Datem 1.200.10 0.05% Emulsifier 12.00 1.00 0.54% L-Cysteine 4.00 0.33 0.18%Calcium Additive² 33.60 2.8 1.52% Calcium Propionate 1.40 0.12 0.06%Gluten 6.00 0.50 0.27%¹All weights are provided in grams.²The calcium additive composition described in Example 8.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The resultingbread contained 330 mg of elemental calcium for each 60 g serving size.The bread had a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

EXAMPLE 13

This Example provides another calcium-fortified white bread made usingthe calcium additive of Example 8. The bread was made with the “liquidsponge” technique using the ingredients listed in Table XI. Thistechnique is similar to the sponge dough technique, however, themajority of the flour is added at the dough stage. In this Example, thecalcium additive was added at the dough stage. TABLE XI % by Flour % byIngredient Sponge¹ Dough Total Weight Weight Flour 506.00 694.00 1200.00100.00 54.43% Water 486.00 127.00 613.00 51.08 27.80% HFCS 219.00 219.0018.25 9.93% Yeast 29.00 18.00 47.00 3.92 2.13% Vegetable Oil 12.54 34.1146.65 3.89 2.13% Salt 5.01 16.47 21.48 1.79 0.97% SSL 3.50 3.50 0.290.16% Datem 1.20 1.20 0.10 0.05% Emulsifier 12.00 12.00 1.00 0.54%Calcium Additive² 0.00 33.60 33.60 2.8 1.52% Calcium Propionate 1.401.40 0.12 0.06% Gluten 6.00 6.00 0.50 0.27%¹All weights are provided in grams.²The calcium additive composition described in Example 8.

The calcium-fortified white bread prepared in this Example was made frompatent flour having a protein content of 11% by weight. The resultingbread contained 330 mg of elemental calcium for each 60 g serving size.The bread had a texture, crumb structure, taste, and “mouth feel”substantially identical to white bread.

The invention having been described by the forgoing description of thepreferred embodiments, it will be understood that the skilled artisanmay make modifications and variations of these embodiments withoutdeparting from the spirit or scope of the invention as set forth in thefollowing claims.

1. A calcium additive for bread dough comprising: (a) an aqueoussolution of an inorganic or an organic acid; and (b) calcium carbonatepowder suspended in said aqueous solution of an inorganic or organicacid; wherein the weight ratio of calcium carbonate to acid is fromabout 4:1 to about 20:1 and the weight ratio of water to the combinedweight of calcium carbonate and acid is from about 1:1 to about 10:1;and wherein the pH of the aqueous solution is from about 3 to about 6.5.2. The calcium additive of claim 1 wherein the acid is an organic acid.3. The calcium additive of claim 2 wherein the organic acid is selectedfrom the group consisting of citric acid, fumaric acid, lactic acid, andmalic acid.
 4. The calcium additive of claim 3 wherein the acid iscitric acid.
 5. The calcium additive of claim 4 wherein the ratio ofcalcium carbonate to citric acid is from about 7:1 to about 15:1 byweight.
 6. The calcium additive of claim 5 wherein the aqueous solutioncomprises water in a weight ratio from about 1:1 to about 5:1 based onthe combined weight of calcium carbonate and citric acid.
 7. The calciumadditive of claim 6 wherein the aqueous solution comprises water in aweight ratio from about 1:1 to about 3:1 based on the combined weight ofcalcium carbonate and citric acid.
 8. The calcium additive of claim 1wherein the pH of the solution is from about 4.0 to about 6.5.
 9. Thecalcium additive of claim 8 wherein the pH of the solution is from about4.5 to about 5.6.
 10. The calcium additive of claim 1 wherein thecalcium carbonate is provided as a powder having a mean particlediameter from about 0.05 μm to about 30 μm.
 11. The calcium additive ofclaim 10 wherein the calcium carbonate is provided as a powder having amean particle diameter from about 10 μm to about 15 μm.
 12. A method forpreparing a calcium additive comprising the steps of: (a) providing anaqueous solution of an inorganic or an organic acid; (b) providingcalcium carbonate powder suspended in said aqueous solution of aninorganic or organic acid; wherein the weight ratio of calcium carbonateto acid is from about 4:1 to about 20:1 and the weight ratio of water tothe combined weight of calcium carbonate and acid is from about 1:1 toabout 10:1; (c) mixing the resulting suspension of calcium carbonate inan aqueous solution of an inorganic or an organic acid at a mixer speedsufficiently high to maintain the calcium carbonate powder as asubstantial homogenous suspension in said aqueous solution; and (d)allowing the aqueous solution to reach a pH of about 3 to about 6.5. 13.The method of claim 12 wherein the acid is an organic acid.
 14. Themethod of claim 13 wherein the organic acid is selected from the groupconsisting of citric acid, fumaric acid, lactic acid, and malic acid.15. The method of claim 14 wherein the acid is citric acid.
 16. Themethod of claim 15 wherein the ratio of calcium carbonate to citric acidis from about 7:1 to about 20:1 by weight
 17. The method of claim 16wherein the aqueous solution comprises water in a weight ratio fromabout 1:1 to about 5:1 based on the combined weight of calcium carbonateand citric acid.
 18. The method of claim 17 wherein the aqueous solutioncomprises water in a weight ratio of about 1:1 to about 3:1 based on thecombined weight of calcium carbonate and citric acid.
 19. The method ofclaim 12 wherein the calcium carbonate is provided as a powder having amean particle diameter from about 0.05 μm to about 30 μm.
 20. The methodof claim 13 wherein the calcium carbonate is provided as a powder havinga mean particle diameter from about 10 μm to about 15 μm.
 21. A methodof fortifying dough with calcium comprising the steps of: (a) providinga calcium additive comprising: (i) an aqueous solution of an inorganicor an organic acid; and (ii) calcium carbonate powder suspended in saidaqueous solution of an inorganic or organic acid; wherein the weightratio of calcium carbonate to acid is from about 4:1 to about 20:1 andthe weight ratio of water to the combined weight of calcium carbonateand acid is from about 1:1 to about 10:1; and wherein the pH of theaqueous solution is about 3 to about 6.5; and (b) incorporating thecalcium additive into a dough.
 22. The method of claim 21 wherein theacid is an organic acid.
 23. The method of claim 22 wherein the organicacid is selected from the group consisting of citric acid, fumaric acid,lactic acid, and malic acid.
 24. The method of claim 23 wherein the acidis citric acid.
 25. The method of claim 24 wherein the ratio of calciumcarbonate to citric acid is from about 7:1 to about 15:1 by weight. 26.The method of claim 25 wherein the aqueous solution comprises water in aweight ratio from about 1:1 to about 5:1 based on the combined weight ofcalcium carbonate and citric acid.
 27. The method of claim 26 whereinthe aqueous solution comprises water in a weight ratio of about 1:1 toabout 3:1 based on the combined weight of calcium carbonate and citricacid.
 28. The method of claim 21 wherein the calcium carbonate isprovided as a powder having a mean particle diameter from about 0.05 μmto about 30 μm.
 29. The method of claim 28 wherein the calcium carbonateis provided as a powder having a mean particle diameter from about 10 μmto about 15 μm.
 30. The method of claim 21 wherein the dough comprises aleavening agent.
 31. The method of claim 30 wherein the leavening agentis yeast.
 32. The method of claim 38 wherein the dough has a final pH ofabout 3.0 to about 6.0.
 33. The method of claim 21 wherein the mixtureis added to the dough in an amount from about 1 to about 10% by flourweight based on the total weight of flour.
 34. The method of claim 21wherein the aqueous mixture is added to one of the group consisting of:the sponge in a sponge dough process, the dough in a sponge doughprocess, the dough in a straight dough process, the dough in a liquidferment process, the dough in a no-time dough process, or the dough in acontinuous mix process.
 35. Dough prepared by the method of claim 21.36. A calcium fortified baked product comprising elemental calcium fromabout 0.1% to about 2.2% by weight, wherein the baked product comprisesflour that is substantially free of bran and wheat middlings, andwherein the baked product has a pH from about 3.0 to about 6.5.
 37. Thecalcium fortified baked product of claim 36 wherein the bread has a pHof about 4.0 to about 5.8.
 38. The calcium fortified baked product ofclaim 37 wherein the bread has a pH of about 5.0 to about 5.4.
 39. Thecalcium fortified baked product according to claim 36, wherein the breadproduct is selected from the group consisting of: a white bread, a wheatbread, a hamburger bun, a roll, a bagel, a pizza crust, a snack food, aDanish, and a muffin.
 40. The calcium fortified baked product accordingto claim 39, wherein the bread product is selected from the groupconsisting of: a white bread, a hamburger bun, and a roll.
 41. Thecalcium fortified baked product of claim 40 comprising calcium fromabout 0.8% to about 1.2% by weight.
 42. A method of fortifying ahamburger bun with calcium the steps of: (a) providing a calciumadditive comprising: (i) an aqueous solution of citric acid; and (ii)calcium carbonate powder suspended in said aqueous solution of citricacid; wherein the weight ratio of calcium carbonate to citric acid isfrom about 4:1 to about 20:1 and the weight ratio of water to thecombined weight of calcium carbonate and citric acid is from about 1:1to about 10:1; and wherein the pH of the aqueous solution is about 3 toabout 6.5; (b) providing a hamburger bun dough comprising wheat flour;and (c) incorporating said calcium additive into said hamburger bundough in a quantity sufficient to provide a hamburger bun upon bakinghaving an elemental calcium content from about 0.1% to about 2.2% byweight of the hamburger bun.
 43. The method of claim 42 wherein saidcalcium additive is incorporated into said hamburger bun dough in aquantity sufficient to provide a hamburger bun upon baking having anelemental calcium content from about 0.8% to about 1.8% by weight of thehamburger bun.
 44. The method of claim 43 wherein said calcium additiveis incorporated into said hamburger bun dough in a quantity sufficientto provide a hamburger bun upon baking having an elemental calciumcontent from about 1.0% to about 1.2% by weight of the hamburger bun.45. The method of claim 42 wherein the aqueous solution comprises waterin a weight ratio from about 1:1 to about 5:1 based on the combinedweight of calcium carbonate and citric acid.
 46. The method of claim 45wherein the aqueous solution comprises water in a weight ratio of about1:1 to about 3:1 based on the combined weight of calcium carbonate andcitric acid.
 47. The method of claim 42 wherein said wheat flourcomprises patent flour.